Analysis of the nonisothermal crystallization kinetics in three linear aromatic polyester systems

Melt or cold crystallization kinetics has a strong bearing on morphology and the extent of crystallization, which significantly affects the physical properties of polymeric materials. Nonisothermal crystallization kinetics are often analyzed by the classical Johnson–Mehl–Avrami–Kolmogorov (JMAK) model or one of its variants, even though they are based on an isothermal assumption. As a result, during the nonisothermal (e.g. constant heating or cooling rate) crystallization of polymeric material, different sets of model parameters are required to describe crystallization at different rates, thereby increasing the total number of model parameters. In addition, due to the uncorrelated nature of these model parameters with the cooling or heating rate, accurate modeling at any intermediate condition is not possible. In the present work, these two limitations of the conventional approach have been eliminated by exhibiting the existence of a functional relationship between cooling or heating rate and effective activation energy during nonisothermal melt or cold crystallization in three linear aromatic polyesters. Furthermore, it has been shown that when the JMAK model is used in conjunction with this functional relationship, it is possible to precisely predict the experimental nonisothermal melt or cold crystallization kinetics at any linear cooling or heating rate with a single set of model parameters.     

Influence of the mode of deformation on recrystallisation kinetics in Nickel through experiments,theory and phase field model

Abstract

In this paper, we report the influence of the mode of deformation on recrystallisation kinetics through experiments, theory and a phase field model. Ni samples of 99.6% purity are subjected to torsion and rolling at two equivalent plastic strains and the recrystallisation kinetics and microstructure are compared experimentally. Due to significant differences in the distributions of the nuclei and stored energy for the same equivalent strain, large differences are observed in the recrystallisation kinetics of rolled and torsion-tested samples. Next, a multi-phase field model is developed in order to understand and predict the kinetics and microstructural evolution. The coarse-grained free energy parameters of the phase field model are taken to be a function of the stored energy. In order to account for the observed differences in recrystallisation kinetics, the phase field mobility parameter is a required constitutive input. The mobility is calculated by developing a mean field model of the recrystallisation process assuming that the strain free nuclei grow in a uniform stored energy field. The activation energy calculated from the mobilities obtained from the mean field calculation compares very well with the activation energy obtained from the kinetics of recrystallisation. The recrystallisation kinetics and microstructure as characterised by grain size distribution obtained from the phase field simulations match the experimental results to good accord. The novel combination of experiments, phase field simulations and mean field model facilitates a quantitative prediction of the microstructural evolution and kinetics.     

Expression of Avian Influenza Virus (H5N1) Hemagglutinin and Matrix Protein 1 in Pichia pastoris and Evaluation of their Immunogenicity in Mice

The conventional avian influenza vaccines rely on development of neutralizing antibodies against the HA and NA antigens. However, these antigens are highly variable, and hence there is a need for better vaccine candidates which would offer broader protection in animals. The M1 of avian influenza is another major structural protein that has conserved epitopes that are reported to induce CD8+ T cells and can contribute to protection against morbidity and mortality from influenza. Hence in an effort to study the immune response of rM1 either alone or in combination with rHA, the hemagglutinin (HA) and matrix protein (M1) of A/Hatay/2004/H5N1 strain of avian influenza were expressed in Pichia pastoris as his-tagged proteins and purified through Ni-NTA chromatography. The His-tag was removed using TEV protease cleavage site and the immunogenicity of purified rHA and rM1 either alone or in combination was determined in mice. One group of mice was immunized with 5 μg of purified rHA, the other group was immunized with rM1, and a third group of mice were immunized with 5 μg of rHA and rM1. All the animals were boosted twice, once on 28 days postimmunization (dpi) and the second on 42 dpi. The immune response was evaluated by enzyme-linked immunosorbent assay (ELISA) and hemagglutination inhibition (HI) assay. The group of mice immunized with rHA and rM1 together showed significantly higher immune response against rHA and rM1 than mice immunized with either HA or M1 antigens. The addition of rM1 with rHA resulted in increased HI titer in animals immunized with both the antigens. These results suggest that the HA and M1 expressed in P. pastoris can be utilized in combination for the development of faster and cost-effective vaccines for circulating and newer strains of avian influenza and would aid in combating the disease in a pandemic situation, in which production time matters greatly.     

DNA double-helix-mediated long-range electron transfer

A theoretical analysis based upon large-scale self-consistent Hartree-Fock calculations at a semiempirical quantum theory level (CNDO/S) is performed to investigate long-range electron transfer in a donor-DNA-acceptor molecule, where the donor and acceptor moieties are tethered to the DNA. The π-stacked base pairs are found to dominate the long-range electronic coupling. Despite the π-electron mediated coupling, the exponential distance decay constant of the electron transfer rate is ∼ 1.2–1.6 Å⁻¹, values typical of electron transfer proteins. The calculated long-range electron transfer rate of the order of 10⁶ s⁻¹ for a metal-to-metal distance of 21 Å is found to be in agreement with kinetic measurements by Meade and Kayyem. Based on the current analysis, the π-electrons dominate the long-range electronic coupling interactions in DNA, but they do not lead to one-dimensional molecular wire-like properties. © 1996 John Wiley & Sons, Inc.     

Identifying the greatest team and captain—A complex network approach to cricket matches

We consider all Test matches played between 1877 and 2010 and One Day International (ODI) matches played between 1971 and 2010. We form directed and weighted networks of teams and also of their captains. The success of a team (or captain) is determined by the ‘quality’ of the wins, not simply by the number of wins. We apply the diffusion-based PageRank algorithm to the networks to assess the importance of the wins, and rank the respective teams and captains. Our analysis identifies Australia as the best team in both forms of cricket, Test and ODI. Steve Waugh is identified as the best captain in Test cricket and Ricky Ponting is the best captain in the ODI format. We also compare our ranking scheme with an existing ranking scheme, the Reliance ICC ranking. Our method does not depend on ‘external’ criteria in the ranking of teams (captains). The purpose of this paper is to introduce a revised ranking of cricket teams and to quantify the success of the captains.     

Calculated structural, electronic and optical properties of Ga-based semiconductors under pressure

The structural, electronic and optical properties of GaP, GaAs and GaSb at ambient and under hydrostatic pressure have been calculated using the full potential linear augmented plane wave (FP-LAPW) method. The calculated lattice constant, bulk modulus and its pressure derivative are compared with available experimental data. The first and second order pressure coefficients for the (Γ-Γ) energy gaps and hydrostatic deformation potential shows agreement with measurement. The linear pressure coefficients of the transition (Γ-Γ) increases significantly as anion atomic number increases (GaP→GaAs→GaSb). The magnitude of linear pressure coefficient of the transition (Γ-X) are small and usually negative. The variation of linear pressure coefficient of the transition (Γ-L) are relatively small and follow similar trend as (Γ-Γ). Overall the calculated linear and nonlinear pressure coefficients show good agreement with the experimental data. The obtained dielectric function, refractive index, extinction coefficient and reflectivity are compared with measured data and show qualitatively good agreement.     

Transfer measurements for the Ti+Ni systems at near barrier energies

Large enhancements have been observed in the sub-barrier fusion cross sections for Ti+Ni systems in our previous studies. Coupled channel calculations incorporating couplings to 2⁺ and 3⁻ states failed to explain these enhancements completely. A possibilty of transfer channels contributing to the residual enhancements had been suggested. In order to investigate the role of relevant transfer channels, measurements of one- and two-nucleon transfer were carried out for ^46,48Ti+⁶¹Ni systems. The present paper gives the results of these studies.     

In Situ Electron Microscopy of Poly(ethylene glycol) Crystals Grown in Thin Ionic Liquids Films

Crystals of poly(ethylene glycol) grown in thin films of the room temperature ionic liquid (IL) 1-ethyl-3-methylimidazolium ethyl sulfate were examined by electron microscopy as a first step toward exploiting nonvolatile liquids for nanoscale imaging of solvated/dissolved polymeric materials. The crystals were generated by cooling supported (over surfaces of varied polarity) and freestanding solution films to room temperature. This “open,” that is, without liquid cell, microscopy was performed on unstained, as-grown crystals in the presence of the IL. A variety of nearly two-dimensional crystal morphologies were observed, including rods, fibers, spherulites, compact faceted single crystals, and interconnected networks, with characteristic sizes ranging from tens of nanometers to tens of microns. Electron diffraction patterns for the rods and fibers revealed single crystal-like long-range order. The nature of the IL support little affected the morphology, but film thickness and cooling rate proved important. To assess the role of solvent polarity, crystals were also grown from 1-ethyl-3-methylimidazolium ethyl sulfate mixed with the second IL, the less polar ethyl-tributyl-phosphonium diethyl phosphate; here, although the morphologies were similar to those made with pure IL, fibrillar morphologies were more prevalent. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 478–486     

Non-adiabatic coupling and conical intersection(s) between potential energy surfaces for HeH2 +

By computing the non-adiabatic coupling terms and the adiabatic-to-diabatic transformation angle along closed contours in nuclear configuration space using the CASSCF method and the aug-cc-pVTZ basis set for the lowest three electronic states of HeH₂ ⁺, we explore the conical intersection between states in near collinear and noncollinear geometries, particularly in the C _2v geometry.